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Item Corrosion Resistance of Atomically Thin Graphene Coatings on Single Crystal Copper(MDPI AG, 2024-05) Mahmudul Hasan, Md; Devadig, Ramesh; Sigdel, Pawan; Lipatov, Alexey; Avci, Recep; Jasthi, Bharat K.; Gadhamshetty, VenkataramanaDesigning minimally invasive, defect-free coatings based on conformal graphene layers to shield metals from both abiotic and biotic forms of corrosion is a persistent challenge. Single-layer graphene (SLG) grown on polycrystalline copper (PC-Cu) surfaces often have inherent defects, particularly at Cu grain boundaries, which weaken their barrier properties and worsen corrosion through grain-dependent mechanisms. Here, we report that an SLG grown via chemical vapor deposition (CVD) on Cu (111) single crystal serves as a high-performance coating to lower corrosion by nearly 4–6 times (lower than bare Cu (111)) in abiotic (sulfuric acid) and microbiologically influenced corrosion (MIC) environments. For example, the charge transfer resistance for SLG/Cu (111) (3.95 kΩ cm2) was 2.5-fold higher than for bare Cu (111) (1.71 kΩ cm2). Tafel analysis corroborated a reduced corrosion current (42 ± 3 µA cm−2) for SLG/Cu (111) compared to bare Cu (111) (115 ± 7 µA cm−2). These findings are consistent with the results based on biofilm measurements. The SLG/Cu (111) reduced biofilm formation by 3-fold compared to bare Cu (111), increasing corrosion resistance, and effectively mitigating pitting corrosion. The average depths of the pits (3.4 ± 0.6 µm) for SLG/Cu (111) were notably shallower than those of bare Cu (111) (6.5 ± 1.2 µm). Surface analysis of the corrosion products corroborated these findings, with copper sulfide identified as a major component across both surfaces. The absence of grain boundaries in Cu (111) resulted in high-quality SLG manifesting higher barrier properties compared to SLG on PC-Cu. Our findings show promise for using the presented strategy for developing durable graphene coatings against diverse forms of corrosion.Item Arsenic Exposure Causes Global Changes in the Metalloproteome of Escherichia coli(MDPI AG, 2023-02) Larson, James; Tokmina-Lukaszewska, Monika; Fausset, Hunter; Spurzem, Scott; Cox, Savannah; Cooper, Gwendolyn; Copié, Valérie; Bothner, BrianArsenic is a toxic metalloid with differential biological effects, depending on speciation and concentration. Trivalent arsenic (arsenite, AsIII) is more toxic at lower concentrations than the pentavalent form (arsenate, AsV). In E. coli, the proteins encoded by the arsRBC operon are the major arsenic detoxification mechanism. Our previous transcriptional analyses indicate broad changes in metal uptake and regulation upon arsenic exposure. Currently, it is not known how arsenic exposure impacts the cellular distribution of other metals. This study examines the metalloproteome of E. coli strains with and without the arsRBC operon in response to sublethal doses of AsIII and AsV. Size exclusion chromatography coupled with inductively coupled plasma mass spectrometry (SEC-ICPMS) was used to investigate the distribution of five metals (56Fe, 24Mg, 66Zn, 75As, and 63Cu) in proteins and protein complexes under native conditions. Parallel analysis by SEC-UV-Vis spectroscopy monitored the presence of protein cofactors. Together, these data reveal global changes in the metalloproteome, proteome, protein cofactors, and soluble intracellular metal pools in response to arsenic stress in E. coli. This work brings to light one outcome of metal exposure and suggests that metal toxicity on the cellular level arises from direct and indirect effects.